Method of treating petroleum oil



. the aidof an agent common to each of the Patented Sept.. 23, reza'-@@TTES istantearanr ortica ITMIESW WEIR', 01?' FILLMORE, CALIFORNA.

METHOD or TREA'rrNe' rEraoLnUM ort.

imputation mea-June 11, 1924. seran No. 719,341.

To all 'wlw/mJ t may concem.'

.Be it known that I, JAMES W. Wm, a citizen of the United States,residingat Fillmore,'in the county of Ventura and State ofCalifornia,have invented anew and use-,

'purifying actions.

By well knownmethods petroleum oils .such as lubricating oils have beenpurified,

.for example clarified and decolorized, by

lteringthrough' or agitating the oil with acomminuted clay or earthypurifying ma- .'teri-al such for example as montmorillonite.

It lis found `that after such treatment has been applied to certainpetroleum oils parailin wax remains in the treated oil. In themanufacture of various petroleum products,

it is desirable to free the lubricating oil from the major portion ofthe paraiiin wax line oramorp'hous'form. An object of the presentinvention is to provide a process in which the paraiiin wax maybeseparated from petroleum oils after a purifying action, 'such asaclarifying and decolorizing action; without rinterfering with orsubstantially retarding the speed or f efficiency of such purifyingaction or treatment.A 4 Y vI have found thatv if petroleum oil istreated withfa comminuted clay lor earthy material such as are'wellknown in this'art to rst purify or clarify and decolorize the oilandthen the treating agent left in the."

mixture while the-mass is cooled below the melting point of the paraiiinwax, the paraiin wax will be disseminated throughout the purifying ortreating agent and the oil may theny be separated from the mass byfiltering ata temperature below the melting point of paraiiin wax. Inthis manner I am' able to perform a. plurality of diii'erent .purifying`actions upon theoil through the aid of a substance or agent operating invveach of the purifying reactions and thus which may exist in the oileither in crystal-- provide a puriiied petroleum oil freed from parailinwax without retarding or destroying the efciency of other purifyingaction or reactions. u

'Another object of the invention is to provide a method for separatingparaiiin wax or other `hydrocarbon which solidify orbecome semi-solid attemperatures less than 140 from petroleum oils, which method may becarried out concurrently' with a decolorizing process employing hightemperatures and in which the decolorizing agent acts upon the oil bythe contact or agita-ting method and in which thedecolorizing agentemployed in the contactdecolorizing operation may be' utilized as a waxadherent medium in the dewaxing operation. v

I have also foundthat, when utilizing the purifying or decolorizingagent left remaining intheoil after afprevious purifying action as a waxadherent medium in the sepa- 'ration of paraiiin wax from petroleum:oils` such separation'can be greatly facilitated by the addition offurther "wax yadherent such asv lubricating oil frompetroleum 'oiL'medium, as the wax separation operation Vfrequentlyrequires. a greaterquantity of as diatomaceous'earth,J sand or the' like, the

diatomaceous earth being found oi" particular'value in disseminatingthev` wax'and permitting a separatlon `of, the petroleumoil from thesolid mass.

medium may be, and preferably is; a Amaj terial having nodecolorizingpropertles such In my @pending application. Serial Num' i ber 39QA17,filed June 21, 19201 a process described in vwhich diluted lubricatingoil stock is filtered at/a reduced temperature in ,the 4presence of awaxadherent medium.

The latter medium may vbe any comminuted .solid capablel of permittingor inducing adi hesion of the congealed wax'thereto to separate the oilfrom its paraiin wax content. This invention is an improvement oli-thesaid pending application in that the petroleum oil containing parainfwax 'is'first subjected. to a purifying actioniby contacting oragitating the oil witha purifying'agent which is also operative asa waxadherent medium andfthen` without removal of the purifying agentcontaining the absorbed impurities, chilling the mass and ltering at aaflin wax.

temperature below the melting point ofpar- By so doing the same materialwhich acts as a purifying agent in one puri'- fying operation may act asthe wax adherent lmedium in the dewaxing operatio-n, thus providing aprcess in which a plusl rality of different purifying actions areaccompl'ished on the oil by the same agent at practically the ingaction. f

'In carrying out theoperation of this process, various petroleum oils ordistillates may- A preferred embodiment of the invention' .may bedescribed by reference to the 1ac- ,companying diagrammatical drawings,which illustrate an apparatus by which the invention may be, practicedin conjunction with a purifying operation upon the oil, such as theprocess of clarifying and'improving the color of lubricating oilsdisclosed in United State Letters Patent No. '1,404,374 and 1,404,375.

In the;v drawing, 2 represents a storageA tank for theoil to be treated.'This tank is connected by pipe 3 with a treating tank 4. 53 is aIhopper controlled by valve 54. The tank 4 is provided with a vaporoutlet 5. Pipe 6 .connects the tank 4 with a pump 7, whlch dischargesthrough a pipe 8 connected through a valve 9 to a heater 10, and througha valve 11 to a cooler 12. The heater 10 is connected by means of a pipe13 to a treating tank 4. As shown in the drawing,

the heater 10 is also connected by a pipe,

14 to the pump 7. 15 represents a valve 1n the pipe 14, and A16represents a valve in a pipe 6.

rIhe cooler 12 is connected to a water jacketed receiver 17 by a pipe18. 55 isa stirring device, consisting of paddles connected to a shaft,which is operated by a belt pulley 21 anda motor not shown. 20 is avalve with a pipe leading to a source of diluent' stock not shown. 22 isa hopper, controlled by a slide 23. 26 is a pipe connecting a receiver17 to a pump 28, which discharges through a chiller 30, the flow beingcontrolled by valves 25, 27 and ,31. v29 is a pipe leading from thechiller back to the. suctlon side of a pump 28, controlled by valves 31and 27 32 is a filter press, provided with a screw conveyor 24,`which.is connected to a wash .a screw conveyor 24. cost of effecting onelpurify- This gasoline, alcohol `or the like. the required amountofpurifying agent and tank 37. Pipe 39 leads from the bottom ofa lterpress 32 to a storagetank 40. The pipe 61 connects a diluting tank 60 toa source of diluent not shown, and is controlled by a Valve 62. 59 is apipeleading from a diluting tank to the heater 33, controlled by valve58. The heater 33 is connected to 56 is a stirring device, with paddles,operated by 'a belt from a motor (not shown).

'The washing tank 37 is provided with a vapor outlet pipe 36, controlledby a valve 35.

The washing tank 37 is also provided with a pipe leading Ato sources ofsteam and air Y respectively controlled by valves 44 and 45.

The washing tank 37 is connected to a cooler 43 by a pipe 42. The cooler43 is connected by a pipe 46 t`o a lter press 48. The filter press 48discharges into a hopper 50, 49

,being a scraper. Pipe 47 connects the filter press 48 to a storage-tank 41.

In operation, the tank4 is filledwith al predetermined quantity ofpetroleum oil" stock of the desired viscosity, which may be an acidtreated lubricating oilstockpr any untreated or treated distillate andwhichmay Aor may not be diluted by the addition of a diluent or cutterstock, Asuch as naphtha, To this stock wax adherent medium is added, theagent or medium being supplied from a bin 53c0nltrolled by a slide 54.AThe tank 2 containsi the petroleum 011 stock to be treated, which isconveyed to the pipe 3 in the treating tank4 controlled bya valve. .J

The purifying agent maybe employed for the purpose of first absorbingthe sulphoacids and free mineral lacid which may have been left in theoil from a previous treatment of the oil such as anvacid treatment.

' The purifying agent may thus be employed upon an acid treated oil,from which the acid sludge has been withdrawn, but which has not beenvneutralized, and will purify the oil by removing impurities present inthe original oil and left in the oil by the acid treatment. It ispreferred, however, that the first operation of the process shallbe adecolorizing or clarifying action upon the oil, and the process will bedescribed as applied to such decolorizing operation. It isV intendedthat if it is desired to provide apurifying operation in whichsulpho-acids or the like areremoved, such process'may be accomicoplished by employing a non-neutralized oil which has been acid treatedand this m21-,

teria] carried through the process in substantially the same manner.

may not bepreviously acid treated and then neutralized.

It is understood that bytheterm decolorizing or decolorizingreaction asused in this description or the accompanying claims,

In conducting a ,decolorizlng action the oil selected `mayor referenceis not necessarily made to an action or reaction in which completedecoloriza- 'tion `is carried on, but the term decolorization. isemployed to indicate an improvement or Idecrease 1n color.

For accomphshing the decolorlzing operation, or other purifying actionon the petroleum oil, a mixture of petroleum oil and decolorizing agentis circulated in the treating tank 4 by means of pump 7-, throughtheheater l0, and is raised to the temperature of a rapid decolorizingreaction, preferably above 250o l?.

4l preferv to employ acid treated clay as the` decolorizing agent, suchyfor example as montmorillonite treated. with sulphur-ic acid and Washedwith water, although various decolorizing agents may be employed.

After the mixture has been subjected to the rapid decolorizing reactiona sufficient time tocarry out the decolorization of the oil to thedesired degree,`and before substan` tial oxidation occurs, the mixtureis passed throughthe cooler 12 by means of pump 7 and proper regulationof valves 9, 11, 15 and 'A '16. The 'mixture of oilin the agent is thenorizing agent 4may be employed forthis pur- 4 pose, it is preferable ltoemploy a commin- 'essarily a decolorizing agent, such as a preferablydiatomaceous earth or the like.

uted solid Wax adherent material, not nec? n Such further Wax adherentmedium,l Whenused, is introduced into the receiver 17 from. the hoppen22 by opening the slide 23.

I After the mixture has been cooled'to approximately atmospherictemperature in receve'r 17, the mixture passes to the chiller 30.

The chiller may be of any suitable type,

such, for instance. as an ammoniaor sulphur dioxide refrigerator. Thetempera- `ture of the mixture is reduced in the chiller 30 to below themelting point of the paraffin Wax content of the oil being treated. Thistemperature will vary With different oils. A range of temperaturebetween and -100 F. v\vill be available. It is understood that theparaffin Waxcontent of the oil is substantially solidified at this stateof the treatment, and ldisseminated. through the wax adherent medium,the decolorizing agent acting in this stepy of the process .as a

Wax ladherent medium. .If further inert material has been added, it alsoserves as Wax adherent material.

The mixture passes from the chiller 30'to the filter press 32, The lowtemperature of `the mixture and the solidification 0f its parafiin wax'content greatly impede the filtration of t-he mixture, particularly incase Where no diluent is being employed. -In o-rder to meet thiscondition, a relatively high pressure is built up on the mixture bymeans of ya pressure pump 28. The necessary pressure will vary somewhatWith oils of differ-Y ent viscosity and also with the amount of diluentadded, but generally Will range betiv-een 25 to 500 pounds per squareinch. With a proper pressure, the mixture may be filtered in the filterpress 32 to separate the oil or diluted oil and agent. The agent Willmaintain the solidified paraffin Wax disseminated, and prevent the sameycoating and clogging the filter medium whereby the same might beruptured.

The filtered petroleum oil stock will pass to the storage tank 40through the pipe 39. Tt is found that after the petroleum oil has beenfiltered the decolorizing agent bearing the-adsorbed coloring matter andany added inert Wax adherent medium will maintain the solidifiedparaflin Wax disseminated throughout its mass.` This filter cake passes.into the Washing tank 37. Thereafter the parafiin -Wax may be recoveredfrom the decolorizing agent, if desired. This may be accomplished byadding a heated, relatively low boiling point petroleum distillate, suchas naphtha, lamp oil distillate, or the like, to the agent as it passesinto Washing tank v In the tank 37 the heated loW boiling pointdistillate, mixed With the decolorizing agent containing the paraffinWax, is agitated by mechanical means. The mixture is vmaintained in tank37 until the paraffin Wax The mixturedis 1 dissolves inthe distillate.then passed to the filter 48, Where the distillate and dissolvedparaflin are separated from the decolorizingagent and adsorbed coloringmatter; lThe distillate and dissolved paraflin Wax then pass Ato thereceiver 41.

The distillate is then distilled OE and condensed by well known methods,and the paraffin wax recovered, which thereafter may be tre-ated in anydesired manner to l produce commercial wax or the like. A valuablefeature of practicing the lnventlon as above set forth is found in thefact that the paraffin Wax has'also been clarified and decolorizedduring the treatment in tank 4.'

'It will be appreciated that by means of the above invention thelubricating oil is freed of objectionable parafiin Wax. This isaccomplished concurrently With the clarification and decolorizationtreatment of the o'il. The decolorizing treatment is not retarded, andAits eiliciency remainsl unimpaired.

In themanufacture of lubricating oils havin relatively lowviscosities-that is, viscoslties which do not exceed 330 seconds 100 F.,Sayboltf-it may not be necessary to add a diluent during thedecolorizing and wax extracting operation, in which case the oil emergesfrom the process undiluted and in all respects comparable withtheproduct of former methods of treatment, except that the objectionableparaiiin -wax has been bricating oils at low temperatures -have prac-vtlcally no paraiiin wax solubility, andr that` eliminated. This is madepossible by appreciating and employing the facts that luan ordinarycomminuted decolorizing agent will maintain solidified paraffin waxdisseminated, and permit filtration under high pressure 'at lowtemperature.

By this invention petroleum oil may be subjected to a plurality ofpurifying operations without requiring the purifying agent to be removedfrom the oil after each operation as the same agent-is employed to eiecteach of the'purifying operations. g 'The invention provides aneconomical and convenient means ,of obtaining a superior parattin wax asa by-product of the treatment of petroleum` oils.

This application is a continuation in part of my application SerialNo.1511,546, filed 'October 31, 1921.

The invention 1s not limited to the specific embodiment above setforthas an example to illustrate a preferredprocess, but is of thelscope set forth in the following claims.

I claim:

1. The process of treating mineral lub.

ricating oilsl containingwax to effect both a decolorization there-ofand-a lowering ofthe coldtest thru the aid of a single substance, whichincludes treating the lubricating oil with a comminuted decolorizingagent at a temperature not substantially less than 250 F. to ei'ect adecolorizing of the oil, then cooling the mixture below. the? meltingpointV "of parain wax to congeal the wax throughout the decolorizingagent, and filtering the oil, below the melting point of paraiin wax,from the solid mass.

2. A method of separating paraiiin wax from mineral lubricating oilcontaining the same, which consists in mixing'the oil with a comminutedkdecolorizing agent, cooling the mixture below the melting point ofparaffin wax, iiltering said mixture under a pressure in' excess of 25lbs per square inch, and below the melting point of paraiin wax, andseparating the paraiin wax from the filtered material.

3. A method of treating mineral lubricating oils containing paraiin wax,which consists in mixing the oil with a comminuted decolorizing agent,maintaining the mixture of oil and age-nt at a temperature to eect adecolorizing reaction, cooling the mixture below the melting pointofparain wax, and filtering the mixture below the melting point ofparaiiin wax toseparate the oil from the l agent, adsorbed coloringmatter and paraiiin wax. y

.4. Ametliod of treating mineral lubricating oil, which consists inmixing the oil with a comminutedy clay, maintaining the mixture of oiland clay at a temperature to effect a decolorizing reaction, coolingvthe mixture below the melting polnt ofparaiiin wax, and

filtering the oil under pressure bel-ow the filtered paraiiin wax-fromthe decolorizing agent.

6. A method ofltreating mineral lubricating oil containinglwax, whichconsists in mixing the 'oil with a comminuted decolorizing and waxadherent medium, maintaining the' mixture of oil and said medium at atemperature to effect av decolorizing reaction, cooling the mixturebelow the melty.ing point of paraffin wax. and filtering the mixturebelow the melting point of paraiiin wax to separate the oil from Athesolid mass.

7 A method of treating petroleum oil containing wax, which comprisesmixing the oil with a 4quantityof comminuted decolorizing wax adherentmedium substantially suicient onlykto decolorize the oil and additionalwax-adherent medium, maintaining the oil while mixed with saiddecolorizing wax, and. filtering the mixture below the melting point ofparaiiin waxto separate the oil from the solid mass.

8. The process of treating lminerallubri.-

cating oils containing wax to eii'ect both al loweringof the cold testand a purifying action through the aid ofa purifying and wax-adherentmedium, which includes treating the lubricating oil with a, comminutedpurifyingand wax-adherent, medium at a temperaturel above the meltingpoint of paraiin wax to effect a vpurifying action, then wax-adherentmedium, at a temperature to effect a decolorizing reaction, cool-ing themixture below the melting point of paraflin cooling the mixture belowvthe melting point p of paraffin wax-to congeal the 'wax throughout thepurifying andwax-adherent medium,

and filtering the mixture below the meltinv ppint of paraiin Wax toseparate the o' om the solid mass. 9. The process of treating petroleumoils containing wax to effect both a' deoolorization thereof and alowering of the cold test,

through the aid of a comminuted decolorizing and wax adherent 'mediumand a comminuted non-decolorizing wax adherent medium, which includestreating the petroleum oil with the comminuted decolorizing and waxadherent-medium at a temperature not substantially less than 250 F. toeffect a decolorization of the petroleum oil, cooling below the point ofrapid oxidization, adding thereto a comminuted solid non-decolorizingwax adherent medi-um, then chilling the mixture below the melting pointof parailin Wax, and liltering, the quantity of decolorizing waxadherent medium mixed with the oil being sufiicient vto decolorize theoil but not suiiice'ntgwithout the presence of the addi- .'tional waxadherent material to permit the iltration of the mixture for theseparation of the congealed Wax.

10. A process of treating petroleum oil containing wax, which includesmixing the oil with a comminuted decolorizing and wax adherent mediummixed with the oil being suiiicient to decolorize the oil but notsulficient without the addition of the diatomaceous earth to permit thefiltration of the mixture for the separation of the congealed wax.

11. The process .of dewaxing hydrocarbons containing wax by utilizing ina spent condition a comminuted material previously used in decolorizinghydrocarbons, which consists in mixingv said material with li uidhydrocarbons containing the wax, chil ing thesaid mixture of liquidhydrocarbons and spent comminuted material below the melting point ofthe wax,'the hydrocarbons other than the wax lportions remaining liquid,then separating the uncongealed hydro carbons from the wax andcomminuted material.

12. The process of dewaxing hydrocarbons containing wax by utilizing acomminuted material previously used in decolorizing hydrocarbons whichconsists in combining the hydrocarbons containing the wax with saidpreviously used comminuted material While still in a spent condition anda diluent miscible with the hydrocarbons, chilling the mixture thusproduced to congeal the 'wax upon the comminuted material, thehydrocarbons other than the wax remaining liquid and then separating thechilled associated wax and comminuted ma terial from the liquid mass.

Signed at Fillmore, Calif., this 9th day of May'l 1924.

v J AMES W.

